Method for forming a catalyzed dye system

ABSTRACT

The invention relates to a method for forming a catalyzed dye system. The method includes the successive steps of (1) forming a mixture comprising at least one dye precursor and a catalyst and (2) adding an alkalizer to the mixture, which forms a catalyzed dye system. The dye system may be exposed to hair for less time than standard oxidative dye systems, which is believed to result in reduced damage to hair.

FIELD OF THE INVENTION

The present invention relates to catalyzed hair dyeing systems andmethods which may reduce the time of exposure of hair to oxidative dyetreatments, thereby reducing overall hair damage from the dyeingprocess.

BACKGROUND OF THE INVENTION

Coloring of hair has become an increasingly popular practice. Peopledesire hair coloration for reasons spanning from style choices toachieving more youthful appearances. As people age, the production ofmelanin slows, resulting in hair greying. Melanin can be purposelyaltered by chemical treatments to give lighter shades. The lightening isachieved by oxidizing the melanin pigments, usually with an oxidizingagent in alkaline solution, also called bleaches. Examples of oxidizingagents that can be used are hydrogen peroxide, potassium, sodium orammonium salts of perborate or percarbonate, persulfate andpercarbamide.

Bleaches are also used during oxidative dyeing treatments. Oxidative (or“permanent”) dye compositions comprise “precursor dyes” which are smallmolecules capable of diffusing into the hair. These molecules mainlybelong to three classes of aromatic compounds: diamines, aminophenolsand phenols. They are sufficiently small to diffuse in the hair shaftwhere, once activated by an oxidizing agent such as hydrogen peroxide,they further react with other precursors to form larger coloredcomplexes. Oxidative hair dye compositions commonly contain, in additionto the dye precursors and a source of peroxide, a variety of additionalcosmetic and peroxide stabilizing agents.

Oxidizing agents can activate oxidative dye precursors across a range ofpH. However, it is known that enhanced dye oxidation can be achieved viathe use of a hair-swelling agent (HSA) that can adjust the pH of theoxidizing solution. Such HSA's further enhance the oxidizing and dyeingprocess by swelling the hair fibers to aid both the diffusion of theperoxide and dyeing agents into the hair and enabling faster, morethorough dye oxidization and hair dyeing. Preferred hair-swelling agentsfor adjusting the pH of peroxide hair oxidizing compositions are aqueousalkaline solutions containing ammonia (ammonium hydroxide) ormonoethanolamine (MEA).

Low levels of chelants are routinely used as stabilizers orpreservatives in various oxidizing compositions. For example, EDTA(ethylenediaminetetraacetic acid) is commonly used as a stabilizer inhydrogen peroxide solution, which would otherwise decompose too rapidlyand could not be stored for a long time. Ethylene diaminedissucinnicacid (EDDS) is also known as a good stabilizing agent component toincrease the stability of laundry bleaching products. Amounts as low as0.1% by weight of the oxidizing composition are usually used tostabilize the oxidizing agent contained in the oxidizing compositions.

Oxidative treatments of hair such as bleaching (discoloration) andoxidative dyeing give good results and are very commonly used. They arehowever not without drawbacks. The oxidizing agents used for bleachingand oxidative dyeing damage hair, to some extent. The mechanism by whichdamage is caused to the hair fibers is not perfectly understood.However, it is known that some of the disulphide bonds linking thekeratin chains break in the presence of oxidizing compositions. Repeatedoxidative treatments leave weak, brittle hairs, which have little shineand luster. An enormous effort has been made to address this problem,and various solutions have been proposed.

Today, most dyeing or bleaching compositions are sold with aconditioner, which is applied on hair after the bleaching or dyeingcomposition has been rinsed off Examples of conditioning agents aresilicones, cationic surfactants and cationic polymers. Howeverefficient, conditioners cannot prevent successive chemical treatmentscausing premature hair breakage. In fact, conditioners do not bring thehair back to its initial condition but merely conceal the damage under aprotective layer of the conditioning agent, which only results in animproved feel of the hair.

U.S. Pat. No. 7,686,849 to Forbes et al. addresses the use oforganotitanates as catalysts for oxidative hair color. The patentacknowledges that these organotitanate catalyst are prone to hydrolysis,offering hydrolysis as the reasoning and mechanism for organotitanatesacting as bonding agents. The high pH instability of organotitanates isknown in the literature, academic as well as vendor, and it is fullyexpected that these catalysts will hydrolyze under high pH formulationconditions to make titanium dioxide.

There is an ongoing need to provide hair color with a stabilizedapproach for minimizing or reducing hair damage in an oxidative hair dyesystem.

SUMMARY OF THE INVENTION

The present invention relates to a method for forming a catalyzed dyesystem. The method includes the successive steps of (1) forming amixture comprising at least one dye precursor and a catalyst and (2)adding an alkalizer to the mixture, which forms a catalyzed dye system.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the rates of reaction of the dye system herein at varyingpH levels.

FIG. 2 is a comparative graph, illustrating changes to viscosity vs.shear rate of exemplary compositions herein.

FIGS. 3A-3C show the formula of Example 1, when formulated according toMethod I herein, under increasing magnification (4×, 20×, and 10×,respectively), 24 hours after formulation.

FIGS. 4A-4C show the formula of Example 2, when formulated according toMethod I herein, under increasing magnification (4×, 20×, and 10×,respectively), 24 hours after formulation.

FIGS. 5A-5C show the formula of Example 3, when formulated according toMethod II herein, under increasing magnification (4×, 20×, and 10×,respectively), 24 hours after formulation.

FIGS. 6A-6C show the formula of Example 4, when formulated according toMethod III herein, under increasing magnification (4×, 20×, and 10×,respectively), 24 hours after formulation.

FIG. 7A is a photo of a sample composition according to Example 3,formulated according to Method II herein.

FIG. 7B is a photo of a sample composition according to Example 2,formulated according to Method I herein.

FIG. 8A is a photo of a sample composition according to Example 4,formulated according to Method III herein.

FIG. 8B is a photo of a sample composition according to Example 1.

DETAILED DESCRIPTION OF THE INVENTION

Dye Precursor Compounds

The following conventional primary intermediate and coupler substancesmay be used as the oxidation dye pre-cursor compounds.

As primary intermediate substances the following can be used: standardprimary aromatic amines with an additional free or substituted hydroxyor amino group substituent in the ortho- or para-position, indolederivative compounds or substituted heterocyclic compounds, especiallyfrom the classes of pyrimidines and pyrazoles, such as1,4-diaminobenzene (p-phenylendiamine), 1,4-diamino-2-methylbenzene(p-toluene-diamine), 1,4-diamino-2,6-dimethylbenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene,1,4-diamino-2-chlorobenzene, 4-di(2-hydroxyethyl)amino aniline,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 4-(2-methoxyethyl)aminoaniline, 1,4-diamino-2-(2-hydroxy-ethyl)-benzene,1,3-bis-N-(2-hydroxy-ethyl)-N-(4-amino-phenyl)-amino-2-propanol,2′,2-1,2-ethanediyl-bis(oxy-2,1-ethanediyloxy)-bis-1,4-diaminobenzene,4-amino-phenol, 4-amino-3-methylphenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol,4-amino-2-(2-hydroxyethyl)amino-methylphenol,4-amino-2-(methoxymethyl)-phenol, 5-amino-salicylic acid,2,4,5,6-tetraaminopyrimidine, 2,5,6-tri-amino-4-hydroxy-pyrimidine,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-(4-methylphenyl)methyl-1H-pyrazole,4,5-diamino-1-(4-chloro-phenyl)methyl-1H-pyrazole,4,5-diamino-1-methylpyrazole, 2,5-dimethylpyridine,2-amino-6-methylphenol or 2-amino-5-methyl-phenol, alone or incombination with each other.

Suitable coupler substances include, for example, substitutedm-diaminobenzenes, m-aminophenol, resorcinol derivative compounds,indole derivative compounds, naphthols or substituted heterocycliccompounds can be used, especially from the classes of pyrimidines andpyridines, such as N,N-dimethyl-3-ureidoaniline, 2,6-diamino-pyridine,2-amino-4-(2-hydroxyethyl)amino anisole,2,4-diamino-1-fluoro-5-methyl-benzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di-(2-hydroxyethyl)amino-1,5-dimethoxy-benzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,3-di-(2-hydroxyethyl)-amino aniline,4-amino-1-ethoxy-2-di-(2-hydroxyethyl)amino-benzene,5-methyl-2-(1-methylethyl)phenol, 3-(2-hydroxy-ethyl)amino aniline,3-(2-aminoethyl)amino aniline, 1,3-di-(2,4-diaminophenoxy)propane,2,4-dimethoxy-1,3-diamino-benzene, 2,6-bis-(2-hydroxyethyl)aminotoluene,3-dimethyl-aminophenol, 5-amino-2-methyl-phenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlorophenol,3-diethylaminophenol, 3-amino-2-chloro-6-methyl-phenol, 3-aminophenol,3-(amidomethyl)aminophenol, 5-(2-hydroxy-ethyl)amino-2-methyl-phenol,3-(2-Hydroxyethyl)amino-phenol, 5-amino-2-ethylphenol,5-(3-hydroxypropyl)amino-2-methylphenol,3-(2,3-dihydroxypropyl)amino-2-methyl-phenol,3-(2-hydroxy-ethyl)amino-2-methylphenol,5-(2-hydroxyethyl)amino-1,3-benzodioxole, 1,3-dihydroxybenzene,4-chloro-1,3-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene,3,4-methylendioxybenzene, 3,4-methylendioxyaniline,1-hydroxy-6-bromo-3,4-methylendioxybenzene,5-amino-4-chloro-2-methylphenol, 3,4-diaminobenzoic acid,6-hydroxy-2H-1,4-benzoxazine, 2,7-dihydroxynaphthalene, 1-naphthol,1,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,2,6-dihydroxy-4-methylpyridine, 2,6-dihydroxypyridine,2-methyl-1-naphthol acetate, phenylmethylpyrazolone,2,6-dihydroxy-3,4-dimethylpyridine, 4-hydroxyindole,5,6-dihydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole,2,3-indolidione, 2-amino-3-hydroxypyrimidine or4,5,6-dihydroxy-indoline, alone or in combination with each other.

The composition may contain one or more of the previously named primaryintermediate and coupler substances. These dye compounds, in so far asthey are bases can also be used in the form of their physiologicallycompatible acid addition salts, for example as the hydrochlorides and/orsulfates, or, in so far as they have aromatic OH groups, in the form ofsalts with bases, for example as alkali phenolates.

The oxidation dye pre-cursor compounds are, based on the ready-to-usedye mixture, contained in the oxidation dye composition according to theinvention in a total amount of from 0.001 to 20 percent by weight,preferably in a total amount of from 0.01 to 5 percent by weight of thedye system. The primary intermediate and coupler substances arepreferably used in equimolar amounts. It is however not disadvantageouswhen one of these classes of substances is present in excess withrespect to the other, or vice versa. The primary intermediate andcoupler substance can be present, for example, in a ratio of from about1:0.5 to about 1:2, respectively.

Oxidizing Agent

The present invention includes an oxidizing agent. Exemplary oxidizingagents include, for example, percarbonates, persulfates, organicperacids and organic hydroperoxides. In certain circumstances, molecularoxygen (including air) may also be used. According to the presentinvention, a preferred oxidizing agent is hydrogen peroxide. In oneembodiment, the oxidizing agent may be present at a level of from about0.75 to about 6 percent by weight of the dye system.

Dye Catalyst

The present invention includes at least one metal-containing compoundfor use as a catalyst. The metal-containing compound preferablycomprises at least one inorganic metal compound. Preferred inorganicmetal compounds comprise compounds of d-block transition metals such asscandium, vanadium, chromium, molybdenum, iron, manganese, cobalt,nickel, copper, zirconium and zinc including, but not limited to, theacetates, acetylacetonates, aluminates, bicarbonates, borates, bromates,carbonates, chlorites, cyanides, diethylcitrates, halides,hexafluoroacetylacetonates, hexafluorophosphates, hexafluorosilicates,dihydrogen phosphates, hydrogen carbonates, hydrogen sulfates, hydrogensulfides, hydrogen sulfites, hydroxides, hypochlorites, iodates,nitrates, nitrites, oxalates, oxides, perfluorophthalocyanines,peroxides, phosphates, phthalocyanines, pyrophosphates, silicates,sulfamates, sulfates, sulfides, sulfites, tartrates, tetrafluoroborates,thiocyanates, thiolates, thiosulfates, tosylates and triflates of thesemetals.

Particularly preferred compounds in this context include VBr₃, VCl₂,VCl₃, VCl₄, V2O₃, V2O₄, V₂O₅, VO(SO₄), VOCl₃, VOF₃, V(C₅H₇O₂)₃,VO(C₅H₇O₂)₂, VO(OR)₃, Mo₂(OCOCH₃)₄, Mo(CO)₆, MoCl₃, MoCl₅, MoO₂Cl₂,MoF₆, MoO₂, MoO₃, MoS₂, MoOCl₄, MoSO₄, Mn(OCOCH₃)₂, Mn(OCOCH₃)₂.xH₂O,Mn(C₅H₇O₂)₂, MnBr₂, MnBr₂.xH₂O, MnCO₃, MnCO₃.xH₂O, Mn₂(CO)₁₀, MnCl₂,MnCl₂.xH₂O, MnF₂, MnF₃, Mn(HCO₂)₂.xH₂O, MnI₂, Mn(NO₃)₂, Mn(NO₃)₂.xH₂O,Mn₃O₄, Mn₂O₃, MnO₂, Mn(C₃2H₁₆N₈), MnSO₄, MnSO₄.xH₂O, MnS, Fe(OCOCH₃)₂,Fe(OCOCH₃)₃, FeBr₂, FeBr₃, FeCl₂, FeCl₂.xH₂O, FeCl₃, FeCl₃.xH₂O,Fe(OEt)₃, FeSO₄.NH₃CH₂CH₂NH₃SO₄.4H₂O, Fe₄[Fe(CN)₆]₃, FeF₂, FeF₃,FeF₃.xH₂O, FeI₂, Fe(CH₃CHOHCOO)₂.xH₂O, Fe(NO₃)₃.xH₂O, Fe(C₂O₄).xH₂O,FeO, Fe₂O₃, Fe₃O₄, FePO₄.xH₂O, Fe(C₃₂H₁₆N₈), FeSO₄.xH₂O, FeS,Fe(BF)₄.xH₂O, Fe(SCN)₂, Co(OCOCH₃)₂, Co(OCOCH₃)₂.xH₂O, Co(C₅H₇O₂)₂,Co(C₅H₇O₂)₂.xH₂O, Al₂CoO₄, CoBr₂, CoBr₂.xH₂O, CoCO₃, CoCO₃.xH₂O.Co₂(CO)₈, CoCl₂, COCl₂.xH₂O, CoF₂, Co[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂, Co(OH)₂,Col₂, Co(NO₃)₂, Co(NO₃)₂.xH₂O, Co(O₂O₄), Co(C₂O₄).xH₂O, CoSO₄,CoSO₄.xH₂O, Co(BF₄)₂, Co(BF₄)₂.xH₂O, Co(SCN)₂, Ni(OCOCH₃)₂,Ni(OCOCH₃).xH₂O, Ni(C₅H₇O₂)₂, NiBr₂, NiBr₂.xH₂O, NiCO₃,Ni(CO₃).xNi(OH)₂, NiCl₂, NiCl₂.xH₂O, NiOCoO, Ni[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂,NiF₂, Ni(OH)₂, Nil₂, Ni(NO₃)₂, Ni(NO₃)₂.xH₂O, Ni(C₂O₄), Ni(C₂O₄).xH₂O,NiO₂, NiO₂.xH₂O, Ni(C₃₂H₁₆N₈), Ni(SO₃NH₂)₂, Ni(SO₃NH₂)₂.xH₂O, NiSO₄,NiSO₄.xH₂O, Ni₃S₂, NiZnFe₄O₄, CuOCOCH₃, Cu(OCOCH₃)₂, Cu(OCOCH₃)₂.xH₂O,Cu(C₅H₇O₂)₂, CuBr, CuBr₂, CuCO₃, CuCO₃.Cu(OH)₂, CuCl, CuCl₂, CuCl₂.xH₂O,Cu[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂, CuF₂, CuF₂.xH₂O, Cu(HCO₂)₂, Cu(HCO₂)₂.xH₂O,Cu(OH)₂, Cu₂(OH)PO₄, CuI, CuFe₂O₄, Cu(NO₃)₂, Cu(NO₃)₂.xH₂O, Cu₂O, CuO,Cu(C₃₂H₁₆N₈), Cu₂P₂O₇.xH₂O, CuSO₄, CuSO₄.xH₂O, CuS,CU[O₂CCH(OH)CH(OH)CO₂].xH₂O, Cu(BF₄)₂, Cu(BF₄).xH₂O, Cu(SCN),Zn(OCOCH₃)₂, Zn(OCOCH₃)₂.xH₂O, Zn(C₅H₇O₂)₂, Zn(C₅H₇O₂)₂.xH₂O, ZnBr₂,ZnBr₂.xH₂O, ZnCl₂, ZnF₂, Zn(C₃₂F₁₆N₈), Zn(C₅HF₆O₂)₂, Zn(C₅HF₆O₂)₂.xH₂O,ZnSiF₆.xH₂O, Zn₁₂, ZnFe₂O₄, Zn(NO₃)₂, Zn(NO₃)₂.xH₂O, Zn(C₂O₄),Zn(C₂O₄).xH₂O, ZnO, ZnO.xH₂O, ZnO₂, Zn₃(PO₄)₂, Zn(C₃₂H₁₆N₈), ZnSO₄,ZnSO₄.xH₂O, ZnS, Zn(BF₄)₂, Zn(BF₄)₂.xH₂O, Zr(OCOCH₃)₄,Zr(OCOCH₃)_(x)(OH)_(4-x), Zr(C5H7O2)₄, Zr(C₂₆H₄₄O₁₆), ZrCO₃(OH₂)₂.ZrO₂,ZrC₁₄, ZrF₄, ZrF₄.xH₂O, Zr(HPO₄)₂, Zr(OH)₄, Zrl₄, ZrO(NO₃)₂,ZrO(NO₃)₂.xH₂O, Zr(SO₄)₂, Zr(SO₄)₂.xH₂O, ZrOCl₂ and ZrOCl₂.xH₂O. Thesecompounds may, for example, be applied in combination with readilyavailable amino phenolic compounds, such as p- or m-aminophenol, andoxidizing agents such as hydrogen peroxide.

Alternative metal compounds for use as catalysts comprise salts of thealkali metals of Group 1, such as potassium, or the alkaline earthmetals of Group 2, for example magnesium. Specific examples of suitablesalts include acetates, acetylacetonates, aluminates, bicarbonates,borates, bromates, carbonates, chlorites, cyanides, diethylcitrates,halides, hexafluoroacetylacetonates, hexafluorophosphates,hexafluorosilicates, dihydrogen phosphates, hydrogen carbonates,hydrogen sulfates, hydrogen sulfides, hydrogen sulfites, hydroxides,hypochlorites, iodates, nitrates, nitrites, oxalates, oxides,perfluorophthalocyanines, peroxides, phosphates, phthalocyanines,pyrophosphates, silicates, sulfamates, sulfates, sulfides, sulfites,tartrates, tetrafluoroborates, thiocyanates, thiolates, thiosulfates,tosylates and triflates, such as KAI(SO₄)₂ K₂CO₃, K₃PO₄, KNO₃, KCl,MgSO₄, Mg₃(PO₄)₂, MgCO₃, Mg(NO₃)₂ and MgCl₂.

In certain embodiments of the invention wherein the at least onemetal-containing compound comprises at least one inorganic metalcompound, the catalyst may comprise at least one mineral or clay.Preferred examples of the minerals or clays include anatase, brookite,eudialyte, ilmenite, perovskite, rutile, sabaite, zircon, zirconolite,zircohylite or zirkelite.

When applying the dye systems to hair fibers, it is preferred that theat least one metal-containing compound for use as a catalyst comprisesat least one metal complex comprising at least one organic ligand. It isalso preferred that the at least one dye precursor comprises an aromaticamino compound, a phenolic compound or an amino phenolic compound suchas p- or m-aminophenol, and that the oxidizing agent is hydrogenperoxide.

In the context of the present invention, particularly suitable catalystswhich comprise at least one metal complex comprising at least oneorganic ligand are metal chelates, most particularly zirconium complexescomprising at least one organic ligand. Typical ligands includeoptionally substituted alkyl ligands. A particularly preferred exampleof such a catalyst is aluminum zirconium glycinate (AZG) chelatecomplex.

AZG is particularly preferred relative to titanium-based metalcompounds. Both zirconium and titanium are known to undergo hydrolyticpolymerization (known as olation) to form large molecular weightoligomers. In the case of aluminum zirconium chlorohydrates andglycinates this reaction does not substantially affect catalyticreactivity nor does it fundamentally alter the structure of thematerial. In contrast organotitanates are structurally modified in thisenvironment to form titanium oxide which is catalytically inactive underthese conditions. Accordingly, in one embodiment, the dye catalyst isfree of titanium. And in a further embodiment, the compositions of thepresent invention are free of titanium.

The dye catalyst may be present at a level of from about 0.0001 to 20%by weight of the dye system.

Alkalizer

The present invention may also include an alkalizer. Suitable alkalizersinclude, for example, alkanolamines such as aminomethylpropanol (AMP)and monoethanolamine (MEA). A particularly preferred alkalizer isammonia.

Alkalizers are known in the art of dying hair for the purpose of raisingthe cuticle of the hair to facilitate delivery of dye compounds belowthe cuticle. While efforts have been undertaken to avoid ammonia,primarily, due to its smell and perception of hair damage, it has beenfound that the combination of an alkalizer with the catalyst, herein,increases the rate of reaction and may therefore reduce hair damage.

It has also been found that the present invention functionsadvantageously at a pH of about 9 or greater. Therefore, the alkalizerherein may be used as a pH adjuster, to facilitate a pH at or aboveabout 9. Preferably, the pH of the present invention is from about 9 toabout 10.

Preferably, the alkalizer may be present at a level of from about 0.1 to25 percent by weight of the dye system.

FIG. 1 shows the rates of reaction of the dye system herein at varyingpH levels. The self-coupling reaction of m-aminophenol (3.0 mmol)mediated by hydrogen peroxide (5 eq) in water (20 mL) was monitored byUV-vis spectroscopy at various pH values (adjusted with HCl or NH₄OH) inthe presence of 5 mol % aluminum zirconium pentachlorohydrex (Rezal 67,SummitReheis). The rates of absorption are directly proportional to thepH of the dye system, including the catalyst herein. For example, at pH8.97 (about pH 9), the rate of absorption is more than double the rateof absorption at pH levels below 6.61. Therefore, the catalyst hereinoperates synergistically with the pH level to determine the rate ofabsorption. Accordingly, at a pH level at about 9 or above, the dyeingprocess occurs faster than at pH levels below, for example, 6.61.

Thickening Agents

Thickening agents, including thickener or gelling agents, includesubstances which can increase or control the viscosity of a composition.Thickeners include those that can increase the viscosity of acomposition without substantially modifying the efficacy of the activeingredients within the composition. Thickeners can also increase thestability of compositions.

Non-limiting examples of thickening agents that can be used in thecontext of the present invention include carboxylic acid polymers,crosslinked polyacrylate polymers, polyacrylamide polymers,polysaccharides, and gums. Examples of carboxylic acid polymers includecrosslinked compounds containing one or more monomers derived fromacrylic acid, substituted acrylic acids, and salts and esters of theseacrylic acids and the substituted acrylic acids, wherein thecrosslinking agent contains two or more carbon-carbon double bonds andis derived from a polyhydric alcohol (see U.S. Pat. Nos. 5,087,445;4,509,949; 2,798,053; CTFA International Cosmetic Ingredient Dictionary,Fourth edition, 1991, pp. 12 and 80). Examples of commercially availablecarboxylic acid polymers include carbomers, which are homopolymers ofacrylic acid crosslinked with allyl ethers of sucrose or pentaerytritol(e.g., Carbopol™ 900 series from B. F. Goodrich).

Non-limiting examples of crosslinked polyacrylate polymers includecationic and nonionic polymers. Examples are described in U.S. Pat. Nos.5,100,660; 4,849,484; 4,835,206; 4,628,078; 4,599,379.

Non-limiting examples of polyacrylamide polymers (including nonionicpolyacrylamide polymers including substituted branched or unbranchedpolymers) include polyacrylamide, isoparaffin and laureth-7, multi-blockcopolymers of acrylamides and substituted acrylamides with acrylic acidsand substituted acrylic acids.

Non-limiting examples of polysaccharides include cellulose,carboxymethyl hydroxyethylcellulose, cellulose acetate propionatecarboxylate, hydroxyethylcellulose, hydroxyethyl ethylcellulose,hydroxypropylcellulose, hydroxypropyl methylcellulose, methylhydroxyethylcellulose, microcrystalline cellulose, sodium cellulosesulfate, and mixtures thereof. Another example is an alkyl substitutedcellulose where the hydroxy groups of the cellulose polymer arehydroxyalkylated (preferably hydroxyethylated or hydroxypropylated) toform a hydroxyalkylated cellulose, which is then further modified with aC₁₀-C₃₀ straight chain or branched chain alkyl group through an etherlinkage. Other useful polysaccharides include scleroglucans comprising alinear chain of (1-3) linked glucose units with a (1-6) linked glucoseevery three unit.

Non-limiting examples of gums that can be used with the presentinvention include acacia, agar, algin, alginic acid, ammonium alginate,amylopectin, calcium alginate, calcium carrageenan, carnitine,carrageenan, chitosan, dextrin, gelatin, gellan gum, guar gum, guarhydroxypropyltrimonium chloride, hectorite, hyaluroinic acid, hydratedsilica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp,locust bean gum, natto gum, potassium alginate, potassium carrageenan,propylene glycol alginate, sclerotium gum, sodium carboxymethyl dextran,sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof.

Further non-limiting examples of thickening agents include carbomer,cetyl alcohol, ammonium acryloydimethyltaurate/VP copolymer, aluminumstarch actenylsuccinate, cocamidopropyl betaine, PPG-2 hydroxyethylcoco/isostearamide, tin oxide, hexadecane copolymer, calcium aluminumborosilicate, alumina, calcium sodium borosilicate, aluminum calciumsodium silicate, synthetic fluorphlogopite, dipropylene glycol,polyethylene glycol, quaternium-90 bentonite, kaolin, and disodium EDTA.

NON-LIMITING EXAMPLES

The following Examples illustrate specific embodiments of thecompositions of the present invention, but are not intended to belimiting thereof. Other modifications can be undertaken by the skilledartisan without departing from the spirit and scope of this invention.

The compositions illustrated in the following Examples are preparedaccording to the methods described hereinafter. All exemplified amountsare listed as weight percents and exclude minor materials such asdiluents, preservatives, color solutions, imagery ingredients,botanicals, and so forth, unless otherwise specified.

The following are representative of dye system of the present invention:

1 2 3 4 5 6 7 8 Phase A Water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.Catalyst¹ — 2.24 2.24 2.24 2.24 2.24 2.24 2.24 Jaguar S — — — — — — —1.00 Butylene glycol — — — — — 5.00 — 5.00 Decyl glucoside 5.00 5.005.00 5.00 5.00 — 5.00 Glycerine 2.00 2.00 2.00 2.00 2.00 5.00 2.00 2.00Lauramidopropyl betaine — — — — — 2.00 — — Erhythorbic acid 0.2  0.2 0.2  0.2  0.2  0.2  0.2  0.50 Tetrasodium EDTA 0.40 0.40 0.40 0.40 0.404.2  0.40 1.00 Sodium sulfite 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.50Arginine — — — — — 2.00 — — p-aminophenol 0.20 0.20 0.20 0.20 — — — 0.504-amino-2-hydroxytoluene 0.22 0.22 0.22 0.22 1.50 1.50 — —2,4-diaminophenoxy — — — — 1.46 1.46 0.10 — ethanol 4-amino-m-cresol — —— — — — 0.30 — p-aminophenol — — — — — — 0.50 m-aminophenol — — — — — —0.60 0.25 tetraaminopyrimidine — — — — — — 0.10 — sulfate Resorcinol — —— — — — 0.50 — Phase B Peg-40 hydrogenated — — — — — 3.00 — — castor oilCocamide MEA 5.00 5.00 5.00 5.00 10.00  — — — Glyceryl Stearate/PEG-100— — — — — 1.50 — — Stearate² Glyceryl Stearate 4.00 4.00 4.00 4.00 4.00— — — Cetearyl alcohol 2.50 2.50 2.50 2.50 2.50 4.00 — — Steareth-212.50 2.50 2.50 2.50 3.00 — — — Candellila wax 2.00 2.00 2.00 2.00 2.00 —— — Oleic acid 1.00 1.00 1.00 1.00 1.00 9.00 — — Sorbitan oleate — — — —— 3.00 — — Sunflower oil — — — — — 2.00 — — Phase C Ammonium hydroxide6.9  6.9  6.9  6.9  4.5  6.4  — — Aminomethyl propanol — — — — — — 8.7 8.5  ¹Aluminum Zirconium Glycinate, available from SummitReheis ²SPARLACEL 165-MBAL-PW-(AP), available from CrodaMethods for Forming the Dye System

The components of the dye system may be combined according to a varietyof conditions. Exemplary methods for forming the dye system aredescribed hereinafter.

For the purpose of comparison, Example 1, provided above, illustrates adye composition which is absent of the catalyst of the presentinvention. This formula may be prepared according to the followingmethod.

Method for Formulating a Dye System without a Catalyst

Example 1 is formed according to the following method. Phase A isprepared by adding the water, decyl glucoside, and glycerine to a beakerwith moderate stirring using a propeller. Once homogeneous, theerythorbic acid, tetrasodium EDTA, and sodium sulfite are added. Themixture is then heated to 80° C. At approximately 70° C. thep-aminophenol and 4-amino-2-hydroxytoluene are added with an increase instirring rate to aid dissolution.

Phase B is prepared by weighing the components into a single beaker andheating to 80° C. on a hot plate.

Once both phases have reached 80° C. they are combined and the heat isremoved, allowing this system to cool.

Once the mixture has cooled to 35° C. the ammonium hydroxide of Phase Cis combined with the mixture of Phases A and B, with vigorous mixing,until a thickened homogeneous emulsion is obtained. The final emulsionis then transferred to suitable containers for later use.

Methods for Forming a Dye System Including a Catalyst

Examples 2-8, herein above, are illustrative of dye systems whichinclude a catalyst according to the present invention. Various methodsfor formulating such dye systems are provided hereinafter.

Method I

Example 2 is prepared according to the following method. Phase A isprepared by adding the water, decyl glucoside, and glycerine to a beakerwith moderate stirring using a propeller. Once homogeneous, theerythorbic acid, tetrasodium EDTA, and sodium sulfite are added. Themixture is then heated to 80° C. At approximately 70° C. thep-aminophenol and 4-amino-2-hydroxytoluene are added with an increase instirring rate to aid dissolution.

Phase B is prepared by weighing the components into a single beaker andheating to 80° C. on a hot plate.

Once both phases have reached 80° C. they are combined and the heat isremoved, allowing this system to cool.

In this example, once the mixture has cooled to 40° C. the AZG catalystis added to the mixture. After the mixture has further cooled to 35° C.the ammonium hydroxide of Phase C is combined with the mixture of PhasesA and B, with vigorous mixing, until a thickened homogeneous emulsion isobtained. The final emulsion is then transferred to suitable containersfor later use.

Method II

Example 3 is prepared according to the following method. Phase A isprepared by adding the water, decyl glucoside, and glycerine to a beakerwith moderate stirring using a propeller. Once homogeneous, theerythorbic acid, tetrasodium EDTA, and sodium sulfite are added. Themixture is then heated to 80° C. In this example, at approximately 70°C. the AZG catalyst is added to the aqueous phase. This is accompaniedby a change in haziness of the liquid. Once homogeneous thep-aminophenol and 4-amino-2-hydroxytoluene are added with an increase instirring rate to aid dissolution.

Phase B is prepared by weighing the components into a single beaker andheating to 80° C. on a hot plate.

Once both phases have reached 80° C. they are combined and the heat isremoved, allowing this system to cool.

Once the mixture has cooled to 35° C. the ammonium hydroxide of Phase Cis combined with the mixture of Phases A and B, with vigorous mixing,until a thickened homogeneous emulsion is obtained. The final emulsionis then transferred to suitable containers for later use.

Method III

Example 4 is prepared according to the following method. Phase A isprepared by adding the water, decyl glucoside, and glycerine to a beakerwith moderate stirring using a propeller. Once homogeneous, theerythorbic acid, tetrasodium EDTA, and sodium sulfite are added. Themixture is then heated to 80° C. At approximately 70° C. thep-aminophenol and 4-amino-2-hydroxytoluene are added with an increase instirring rate to aid dissolution.

Phase B is prepared by weighing the components into a single beaker andheating to 80° C. on a hot plate.

Once both phases have reached 80° C. they are combined and the heat isremoved, allowing this system to cool.

Once the mixture has cooled to 35° C. the ammonium hydroxide of Phase Cis combined with the mixture of Phases A and B, with vigorous mixing,until a thickened homogeneous emulsion is obtained. Finally, the AZGcatalyst is added slowly to the thickened emulsion. Once addition iscomplete and homogeneous the final emulsion is then transferred tosuitable containers for later use.

Examples 2-4 are identical to one another regarding their overallingredient list, but are formulated according to the discrete methodsdiscussed hereinabove. Examples 5-8 are provided for furtherillustrative purposes, and may be prepared according to any of themethods described herein. Each of examples 2-4 differ from Example 1 inthat Example 1 does not include a catalyst, and therefore is alsoformulated according to a different method. FIG. 2 illustrates theimpact of addition of the catalyst to the base formula on its viscosity.According to formulation Methods I and II, the addition of the catalystincreases the overall viscosity of the dye system. These methods resultin enhanced spreadability and even distribution of the catalyst systemherein. However, the technique described in Method III fails to achievethe viscosity benefits of Methods I and II. Therefore, it has been foundthat addition of an alkalizer, such as NH₃, before the catalyst isintroduced, results in uneven distribution of the catalyst.

FIGS. 3A-3C show the formula of Example 1, under increasingmagnification (4×, 20×, and 10×, respectively), 24 hours afterformulation. The orientation of the dye structure is believed tocorrelate to the viscosity profile of Example 1 illustrated in FIG. 3.As the dye system thickens, the structure becomes increasingly dense.

FIGS. 4A-4C show the formula of Example 2, when formulated according toMethod I herein, under increasing magnification (4×, 20×, and 10×,respectively), 24 hours after formulation. As is illustrated in thesedepictions, the dye system is more dense, with an even distribution ofthe catalyst.

FIGS. 5A-5C show the formula of Example 3, herein, under increasingmagnification (4×, 20×, and 10×, respectively), 24 hours afterformulation. As is illustrated in these depictions, the dye systemformulated according to Method II results in a dense consistency.

FIGS. 6A-6C show the formula of Example 4, under increasingmagnification (4×, 20×, and 10×, respectively), 24 hours afterformulation. As is illustrated in these depictions, the dye systemformulated according to Method III results in a structure that generallyconforms to the dye system depicted in FIGS. 3A-3C. Therefore, nothickening benefit results from application of Method III.

FIGS. 7A, 7B, and 8B show the dye system having a homogeneousconsistency. FIGS. 7A and 7B particularly show a thickened system,containing a homogeneous distribution of the catalyst herein.

In contrast, FIG. 8A shows a heterogeneous system, with interspersedclusters of the catalyst herein. This system results in an unevendistribution of the catalyst, creating catalytic “hot zones” with thesystem, which is unsuitable for controlled application of the catalystsystem to hair. This further demonstrates the drawbacks of alkalizingthe system before addition of the catalyst, as described by Method IIIherein.

Example

Furthermore, in view of the enhanced rate of reaction achieved via theformulas herein, known sensitizers such as paraphenylenediamine (PPD)and paratoluenediamine (PTD) are not essential to the dye systemsherein. Therefore, in one embodiment, the dye system herein is free fromPPD or PTD.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method for forming a catalyzed dye systemcomprising the successive steps of: (a) forming a mixture comprising atleast one dye precursor and a catalyst; and (b) adding an alkalizer tosaid mixture, to form said catalyzed dye system; wherein said catalystis aluminum zirconium glycinate.
 2. A method according to claim 1,wherein said catalyzed dye system further comprises at least onethickening agent.
 3. A method according to claim 1, wherein saidcatalyzed dye system further comprises water.
 4. A method according toclaim 1, wherein said alkalizer is selected from the group consisting ofaminomethylpropanol, monoethanolamine, and ammonium hydroxide.
 5. Amethod according to claim 1, wherein said dye precursor is substantiallyfree of paraphenylenediamine, paratoluenediamine, and combinationsthereof.